- 1State Key Laboratory of Chemical Engineering, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China
- 2Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China
- 3Department of Chemical and Environmental Engineering, University of California, Riverside, Riverside, CA, United States
Association between cations and anions plays an important role in the interfacial structure of room-temperature ionic liquids (ILs) and their electrochemical performance. Whereas great efforts have been devoted to investigating the association effect on the equilibrium properties of ILs, a molecular-level understanding of the charging dynamics is yet to be established. Here, we propose a theoretical procedure combining reaction kinetics and the modified Poisson-Nernst-Planck (MPNP) equations to study the influences of ionic association on the dynamics of electrical double layer (EDL) in response to an applied voltage. The ionic association introduces a new decay length λS and relaxation time scale
Introduction
Room-temperature ionic liquids (ILs) have been broadly explored as promising electrolytes in various fields of electrochemistry (Xiao and Johnson, 2003; Sato et al., 2004; Wang, 2020) including both batteries (Lee et al., 2006; Rupp et al., 2008) and supercapacitors (Ue et al., 2003; Zhou et al., 2004; Arunachalam et al., 2020; Tao et al., 2020). Understanding their charging dynamics, i.e., the polarization of ionic distributions in response to a biased electrical potential, is desirable for many electrochemical applications (Zhang et al., 2020; Tao et al., 2021; Tao et al., 2022). Although the structure and thermodynamic properties of ILs in the electric double layer (EDL) have been widely studied (Chen et al., 2021a; Chen et al., 2021b; Gan et al., 2021; Wang et al., 2021), the dynamic behavior remains poorly understood in particular on how association between cations and anions influences charge relaxation and ion transport under confinement.
In comparison to that of an aqueous electrolyte solution, the relative permittivity of ILs is extremely small (∼2), implying the prevalence of ion pairing due to the strong electrostatic attraction between cations and anions (Wang and Voth, 2005; Canongia Lopes and Pádua, 2006; Fraser et al., 2007; Niedermeyer et al., 2012). From a thermodynamic perspective, the ionic association may be described in terms of a chemical reaction (Figure 1A):
where the association constant is related to the kinetic parameters for the forward and backward reactions,
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FIGURE 1. (A) Formation of a neutral particle by cation-anion association. (B) A cartoon sketch for the distribution of ionic species between two parallel electrodes. (C) An instantaneous increase of the electrical potential on the electrode surface located at position L.
In previous work (Jiang et al., 2014; Lian et al., 2016; Ma et al., 2022), we studied the dynamic behavior of room-temperature ionic liquids using a time-dependent density functional theory (TDDFT) that accounts for the ionic excluded volume effects, electrostatic correlations, and short-range attractions. We found that the electrokinetic behavior of ionic liquids is distinctively different from that predicted by the conventional equivalent-circuit (EC) models or theoretical methods based on the Poisson-Nernst-Planck (PNP) equations. While the EC model predicts a monotonic increase of the surface charge density upon the application of a biased voltage, TDDFT calculations indicate that there exist three types of charging behavior depending on the degree of confinement and the magnitude of the biased potential. A monotonic increase of the surface charge density occurs only when its equilibrium value has a sign the same as that of the applied voltage; kinetic charging inversion takes place when the equilibrium charge is below or opposite of the asymptotic charge density. The non-monotonic charging behavior was also reported for the response of a monomeric layer of ionic liquids in slit pores (Kondrat and Kornyshev, 2013). In addition to theoretical studies, the dynamics of EDL charging has been examined by a number of theoretical studies based on molecular dynamics (MD) simulations (Mceldrew et al., 2020; Mceldrew et al., 2021a; Mceldrew et al., 2021b). To our knowledge, the effects of ionic association have not been explicitly examined in spite of its apparent importance in determining the properties of ILs.
In this work, we proposed a set of reaction-coupled modified PNP (RC-MPNP) equations to describe the charging behavior of ILs near electrodes. Similar to TDDFT, RC-MPNP employs a local electrochemical potential as the driving force for the evolution of the density profiles of ionic species in response to an applied voltage. In comparison to alternative methods, its main advantage is that the dynamic equations for electric migration, diffusion, and chemical reaction can be solved self-consistently at time and length scales beyond those that could be achieved with TDDFT or MD simulation. Importantly, RC-MPNP allows us to study the ionic pairing effects on the dynamic structure and local physicochemical properties of ILs under an electrical field, including the density distributions of all ionic species (cations, anions and ion pairs), charge relaxation, as well as the relationship between various characteristic timescales, decay length and association strength. The theoretical results also reveal how ionic association affects the capacitance and resistance of ILs during the charging process.
Molecular Model and Theory
Model Description
As shown schematically in Figure 1A, association between cations and anions can be written in terms of a reversible reaction, i.e., one anion reacts with one cation to form a neutral particle labeled as m. At equilibrium, the fraction of neutral particles is determined by association constant K through the law of mass action. In the presence of an electric field, the equilibrium distribution of ionic species depends on the local electrical potential, various forms of non-electrostatic interactions as well as the equilibrium constant.
Figure 1B sketches a cartoon representation of the ionic system considered in this work. For simplicity, we assume that all ionic species, including the neutral ion pairs, can be represented by hard spheres of equal size. While ILs confined between two parallel plates of opposite charge do not reflect the configuration of any specific electrochemical device, the symmetric one-dimensional setup allows us to capture the essential features of charging dynamics for electrolytes near an electrode surface, in particular in terms of the evolutions of the local charge density and ionic density profiles in response to an applied voltage. The relaxation process is coupled with an evolving electric field, particle transport, and association between cations and anions. A realistic model for IL charging should capture all such effects in addition to thermodynamic non-ideality arising from other forms of inter-particle interactions.
Governing Equations and Chemical Potential
Our reaction-coupled modified PNP (RC-MPNP) equations are similar to those proposed by Suzuki who studied charge transport in weak electrolytes (Suzuki and Seki, 2018). The model ionic liquid consists of three kinds of ionic species: cations, anions, and neutral particles generated by cation-anion association. For simplicity, all these ionic species are represented by spherical particles of the same size. To describe the charging dynamics, we start with the continuity and diffusion-reaction equations
where
and
Equations 4, 5 follow the kinetics of ion association, i.e., the change in the local ion concentration reflects a balance of the forward and backward reactions. As mentioned above, the equilibrium constant is related to the rate coefficients
We assume that the intrinsic chemical potential can be obtained by minimizing the grand potential (Detail derivations are given in Supplementary Material). Accordingly, the electrochemical potentials of the ionic species are
where e is the unit charge, a is the diameter of hard spheres, and
where
For simplicity, we assume that the diffusion coefficient and the particle size for ion pairs the same as those for ionic species.
In integration of the continuity equations, we need to solve the following equations simultaneously:
where
Parameter Setting and Boundary Conditions
In describing the charging dynamics, the RC-MPNP equations entail three types of parameters that are affiliated with the system characteristics, boundary conditions and initial values. In this work, we assume that cations, anions and ion pairs have the same size of a = 0.5 nm, i.e., they all occupy a single lattice site. Both cations and anions are monovalent,
In studying the charging dynamics, we assume that a biased potential of
where the initial particle densities are assumed identical to the corresponding bulk values,
Because the bulk concentrations are fixed during the charging process, an explicit consideration of the thermodynamic non-ideality is equivalent to changing the bulk concentration. In the presence of an electric field, the RC-MPNP equations allow us to describe the relaxation of the ionic density profiles until a new equilibrium is established. The time range used in the calculation is from 10–3 τRC to 103 τRC with
Results and Discussion
Time-dependent Density Distributions
The application of a biased potential introduces a local electric field driving ionic motions thereby breaking down the local ionic association equilibrium. Therefore, we expect that the evolution of the ionic density profiles is different from that corresponding to a non-reactive system. Figure 2 shows the variations of the total ionic density (
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FIGURE 2. The evolutions of the total ion density (
Furthermore, Figure 2 shows the influence of ionic association on density distribution. It can be found that with the increase of association strength (i.e., a larger K*), the number densities of cations and anions are dramatically reduced while the number density of neutral particles increases. The ionic association affects the local concentrations of the three types of ionic species (cations, anions and ion pairs) hence the kinetic behavior and other physicochemical properties, such as timescales, capacitance and resistance.
Charge Decay Length
In order to understand the structural relaxation under the influence of ionic association, we need to identify the decay length from the density distributions. The decay length, λS, may be extracted by taking the logarithm of the charge distribution (log|q*|), which yields approximately a straight line at each position as shown in Figure 3. A decay length can be obtained by averaging over the slopes of the straight lines at different positions.
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FIGURE 3. (A) Charge distribution at K* = 1,
Figure 3E presents the evolutions of the decay length λS for ionic liquids with different association constants. The decay length reaches a stable state at τRC approximately independent of K. Note that the dimensionless association constant is defined as
Alternatively, the decay length can be defined in terms of the density profiles of ionic species or neutral particles. Qualitatively, the conclusions are similar. As shown in Supplementary Figure S1, the stronger association that takes place between cations and anions, the longer decay length that we extract according to the evolution of the particle concentrations. While there is only one decay length if K = 0, The two slopes of the density profile allow us to identify two decay lengths at low association strength.
Charge Relaxation Timescale
It has been well established that the PNP equations yield a quantitative relation between the dynamic timescale and the Debye length,
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FIGURE 4. (A) The normalized surface charge density on the electrode plate
Figure 4B plots τ(t) for different association strengths. In the early stage (t/τRC < 1), τ(t) is controlled by the EDL formation, and the characteristic time is represented by τ1. In the case of no association, the RC time is given by
Figure 4C shows a quantitative relation between the decay length λS and the Debye length at a fixed association strength. Empirically, the relation can be fitted by using the following analytical form (R2 > 0.99):
Substituting the above formula into
where a = 0.341 and b = 0.408 are obtained by fitting the numerical results. By comparing
In the later stage of charging (t/τRC > 1), τ(t) shows a step-like behavior with different plateaus τad for different values of K*. In this case, τ(t) is controlled by the particle diffusion, and the dynamics is much slower than electrical motion in the early stage. The ion diffusion can be characterized by the timescale,
where c = 0.109 and d = 1.318. Eqs 16–18 provide convenient estimations of the timescales for different stages of charging under the influence of ionic association.
Qualitatively, the equilibrium and dynamic properties of ionic liquids discussed above are relatively insensitive to the bulk concentration of ionic species (Supplementary Figures S3, S4). While both the bulk concentration and association strength affect the timescales of charging and particle relaxation, it is important to recognize that ionic association is mainly responsible for the increase of decay length and relaxation time.
Conclusion
In summary, we have integrated the modified Poisson-Nernst-Planck (MPNP) equations with the kinetics of inhomogeneous reaction to account for ionic association during electric double layer (EDL) charging. The reaction-coupled MPNP (RC-MPNP) equations were applied to study the charging dynamics of model EDL systems containing in room-temperature ionic liquids (ILs). By extracting the decay lengths and time scales from the evolution of the total local ion density and charge distribution, we found that ionic association has significant effects on the dynamics of EDL charging as characterized by a fast electrical motion at the early stage and a slower ion diffusion in the later stage. Quantitative relations have been established between the two timescales affiliated with the two stages of charging, τ1 and τ2, and the charging decay length λS and association constant K. The generic theoretical framework can be applied to other ionic systems that involve similar association reactions.
Data Availability Statement
The original contributions presented in the study are included in the article/Supplementary Material, further inquiries can be directed to the corresponding authors.
Author Contributions
JC, CL, and JW analyzed the results and wrote the manuscript. All coauthors contribute to the research. CL initiate the original ideas. All authors contributed to the article and approved the submitted version.
Funding
This work was sponsored by the National Natural Science Foundation of China (No. 91834301, 22078088, 21703153, 21808055), the Open Project of State Key Laboratory of Chemical Engineering and the Shanghai Rising-Star Program (No. 21QA1401900). JW thanks the financial support from the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Basic Energy Sciences.
Conflict of Interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Publisher’s Note
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.
Acknowledgments
JC thanks Ms. Zhang Man for her helpful discussion.
Supplementary Material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fceng.2022.852070/full#supplementary-material
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Keywords: room-temperature ionic liquids, ion association, charging dynamics, electrical double layer, Poisson-Nernst-Planck (PNP) equations
Citation: Cheng J, Tao H, Ma K, Yang J, Lian C, Liu H and Wu J (2022) A Theoretical Model for the Charging Dynamics of Associating Ionic Liquids. Front. Chem. Eng. 4:852070. doi: 10.3389/fceng.2022.852070
Received: 10 January 2022; Accepted: 16 February 2022;
Published: 13 April 2022.
Edited by:
Nebojša Zec, German Engineering Materials Science Centre (GEMS) at Heinz Maier-Leibnitz Zentrum (MLZ) Helmholtz-Zentrum Hereon, GermanyReviewed by:
Zhongming Wang, Florida International University, United StatesAleksandar Tot, Royal Institute of Technology, Sweden
Copyright © 2022 Cheng, Tao, Ma, Yang, Lian, Liu and Wu. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
*Correspondence: Cheng Lian, liancheng@ecust.edu.cn; Honglai Liu, hlliu@ecust.edu.cn; Jianzhong Wu, jwu@engr.ucr.edu
†These authors have contributed equally to this work